CN114196099B

CN114196099B - Polyolefin resin foamed sheet and preparation method thereof

Info

Publication number: CN114196099B
Application number: CN202210148575.2A
Authority: CN
Inventors: 魏琼
Original assignee: Basek Adhesive Science & Technology Suzhou Co ltd
Current assignee: Basek Adhesive Science & Technology Suzhou Co ltd
Priority date: 2022-02-18
Filing date: 2022-02-18
Publication date: 2022-05-24
Anticipated expiration: 2042-02-18
Also published as: CN114196099A

Abstract

The invention relates to a polyolefin resin foaming sheet, aiming at solving the problems that the prior polyolefin resin foaming sheet is difficult to simultaneously balance degumming performance and waterproof performance, the research of the invention finds that the ratio of the half-peak width and the peak height of the DSC melting peak of the polyolefin resin foaming sheet is controlled within a certain range, so that the polyolefin resin foaming material can realize good waterproof performance, is difficult to degum, and can simultaneously balance degumming performance and waterproof performance. The polyolefin resin foamed sheet of the present invention is particularly suitable for use in waterproofing electronic devices such as smart mobile communication devices, notebook computers, electronic books, tablet terminals, game devices, cameras, wearable electronic devices, and the like.

Description

Polyolefin resin foamed sheet and preparation method thereof

Technical Field

The present invention relates to a polyolefin resin foamed sheet, and more particularly to a polyolefin resin foamed sheet suitable for use in a waterproof sealing tape for electronic devices.

Background

With the increasing requirements of modern society on environment-friendly materials, polyolefin foam materials gradually replace traditional foam plastics and become indispensable materials for downstream manufacturing industries. The polyolefin foam material may include polypropylene (PP), polyvinyl chloride (PVC), Polyethylene (PE), ethylene-vinyl acetate copolymer (EVA) foam, and the like. The polyolefin foam material has the characteristics of rich raw material sources, light weight, excellent cost performance, excellent heat resistance, chemical corrosion resistance, easy recovery and the like, and is one of the raw materials widely applied in the plastic soft foaming industry.

The polyolefin foaming material is a high molecular material which takes olefin polymers (PE polyethylene, PP polypropylene and the like) as main raw materials, generates a large number of independent fine cells in the material through a complicated foaming process and is uniformly dispersed in a solid material. The polyolefin foam material has a series of characteristics of high resilience, high weather resistance, high insulation, noise reduction and sound insulation, waterproof sealing, heat preservation and heat insulation, small density, easy molding and the like, and is one of the raw materials widely applied in the plastic soft foam industry. By adding other materials, the material also has special performances of antibiosis, antistatic property, flame retardance, skid resistance and the like, and can be used as a functional material in various fields such as building decoration materials, consumer electronics products, automobile interior materials and the like. An electron irradiation crosslinking polyethylene foaming material (IXPE) and an electron irradiation crosslinking polypropylene foaming material (IXPP) belong to the field of polyolefin soft foaming materials. Compared with EVA and PS foam materials, the polyolefin foam material, especially the electron irradiation crosslinking polyolefin foam material has the characteristics of no toxicity, environmental protection, greenness and health, and is widely applied to the fields of environmental building materials, consumer electronics and the like. The continuous growth of downstream market demand in the polyolefin foam industry is expanding the market space in the foam manufacturing industry. The downstream of the industry mainly comprises the industries of building materials, consumer electronics, automobiles and the like, and the growth of the industry is in the future with the continuous and rapid growth of the economy of China.

In the field of consumer electronics, polyolefin foam materials are widely applied to buffer gaskets on the back of screens of smart phones, gaskets of parts such as smart phone cameras and speakers and dustproof gaskets of smart watches, and play roles in sealing, preventing dust, absorbing impact, preventing noise and the like. Nowadays, the characteristics of intellectualization, large-size full screen, double lens, high resolution, water resistance, personalized scene experience, high cruising ability and the like become the most remarkable development direction of consumer electronics products. Consumer electronics are increasingly demanding in terms of cushioning, sealing, shock absorption, water resistance, and the like. In the past, consumer electronics manufacturers have used PET materials to seal between the screen and the housing against water. However, PET materials have a high hardness and limited impact resistance. If the PET adhesive tape is used as a sealing adhesive material between a touch layer and a liquid crystal display layer of a product screen, the screen can generate a water wave phenomenon under external force extrusion.

Polyolefin resin foamed sheets have high impact absorption even when they are thin, and therefore, they are widely used in electronic devices such as smart phones, personal computers, and electronic papers, and are disposed between electronic components and frame members to provide cushioning and sealing effects.

In addition, the polyolefin resin foamed sheet is required to have better impact absorbability, and is also required to be difficult to degum as much as possible, and because the surface energy of the polyolefin foamed sheet is low, the polyolefin resin foamed sheet is easy to degum when being used together with glue, on one hand, the use stability of the polyolefin resin foamed sheet is reduced, and the performances of sealing, water resistance and the like are seriously influenced. On the other hand, the probability of internal damage of the electronic equipment caused by degumming is greatly improved, and the maintenance and use cost of the electronic equipment is greatly improved. Therefore, better adhesion performance is one of the goals that has been pursued in the art. At present, the surface roughness of the foaming material is generally increased by adopting a surface treatment mode to improve the bonding strength, for example, as described in patent document with publication number CN112831282A, the surface treatment agent can be regarded as a bridging agent between the adhered material and the adhesive, and the function of the surface treatment agent is to remove the dirt, oil stain and processing aid on the surface of the adhered material; secondly, a new surface layer can be formed on the surface of the bonded material, and the polarity, activity, roughness and the like of the surface of the bonded material are changed to be matched with the used adhesive, so that the bonding strength is improved. However, surface treatment agents can destroy surface strength, thereby affecting overall performance. And the addition of the surface treating agent additionally increases the cost, thereby having adverse effect on the economic benefit of enterprises.

Further, the portable electronic device sometimes falls into water unintentionally. In addition, in the portable electronic device, water droplets such as rain may adhere. When moisture adheres to a portable electronic device in a large amount, moisture may enter the portable electronic device to cause a display failure. A portable electronic device is required to have high water resistance so that display failure due to moisture does not occur as described above. Therefore, the polyolefin resin foamed sheet is required to have not only good impact absorbability and unsusceptibility to degumming but also good water-repellent properties.

In order to ensure that the polyolefin resin foam material is not easy to degum, the surface roughness of the foam material is generally required to be higher, and the waterproof performance of the material is poor due to the overhigh surface roughness, so how to balance the degum and the waterproof performance of the polyolefin resin foam material is a technical problem to be solved at present.

Disclosure of Invention

In order to give consideration to degumming and waterproof performance of the polyolefin resin foaming material, the invention modulates the polarity difference of different resins with different molecular weights and different types and the proportion difference of different types of resins, and adjusts the preparation conditions of extrusion temperature and rotation speed, crosslinking irradiation energy, irradiation dose and the like in the preparation process to ensure that the ratio of half-peak width to peak height of a DSC melting peak of the finally prepared polyolefin resin foaming material is in a certain range, thereby finally realizing the balance of degumming and waterproof performance.

Thermal analysis is one of the basic methods for characterizing materials and has been widely used in research and industry for many years. In recent years, there have been many developments in various fields, particularly in the field of polymer materials. Thermal analysis has great application value in polyolefin resin research, especially polyolefin resin development, and can be used for not only research and development of products, but also production monitoring, product quality identification and the like. Differential Scanning Calorimetry (DSC) is to make a sample under the control of a certain temperature program (rise/fall/constant temperature), observe the change process of the heat flow power difference between a sample end and a reference end along with temperature or time, so as to obtain the relevant heat effect information of the sample in the temperature program process, such as the change of heat absorption, heat release, specific heat, and the like, and calculate the heat absorption and release amount (heat enthalpy) and the characteristic temperature (start point, peak value, end point) of the heat effect. The DSC method is widely applied to various fields of plastics, rubber, fibers, coatings, adhesives, medicines, foods, biological organisms, inorganic materials, metal materials, composite materials and the like, and can research the melting and crystallization process, glass transition, phase transition, liquid crystal transition, solidification, oxidation stability, reaction temperature and reaction enthalpy of the materials, determine the specific heat and purity of substances, research the compatibility of each component of a mixture, calculate the crystallinity, reaction kinetic parameters and the like. DSC is one of the most widely used thermal analysis techniques, and can be used to characterize the glass transition temperature (Tg), melting temperature (Tm), crystallization temperature (Tc), and oxidation induction period time (OIT) of a high polymer, which can give information on the oxidation behavior of the material and the influence of additives. The melting curve gives information on the degree of crystallinity, the greater the degree of crystallinity, the more perfect and regular the crystallization, and the greater the enthalpy of fusion.

In addition, the relationship between the half-value width of the DSC melting peak and the peak height can reflect the compatibility of the resin in the resin foaming material from the side surface, thereby influencing the surface roughness and the waterproof performance of the polyolefin resin foaming material. If the ratio of the half-peak width to the peak height of the DSC melting peak is low, the resin compatibility is good, the surface roughness is low, and the surface waterproof effect is good, but the low surface roughness can cause the degumming performance of the polyolefin resin foaming material to be reduced, so that the polyolefin resin foaming material is easy to degum. On the other hand, if the ratio of the half-value width of the DSC melting peak to the peak height is high, this means that the compatibility between resins is poor, and the resulting polyolefin resin foam material has a high surface roughness, and although it has an advantage of being not easily degummed, it may cause deterioration in the surface water-repellent performance. Therefore, by controlling the ratio of the half-peak width of the DSC melting peak to the peak height within a certain range, the polyolefin resin foam material can realize good water resistance and difficult degumming, and realizes the balance of degumming and water resistance.

To achieve the above object, the present invention provides a polyolefin resin foamed sheet having a thickness of 0.06 to 1.5mm and a density of 0.1 to 0.8g/cm³A closed cell ratio of 90% or more, a crosslinking degree of 20% to 50%, and a compressive strength at 25% of 50 to 650 kPa; the ratio of half-value width/peak height of DSC melting peak of the foamed sheet is 15 to 71 (DEG C.g/W), preferably 20 (DEG C.g/W) to 50 (DEG C.g/W).

The DSC melting peak test method comprises the following steps:

differential scanning calorimetry is a thermal analysis method for researching the relation between the power difference and the temperature of a sample and a reference substance, can be used for measuring the reaction heat, the crystallinity, the phase change and the like of a material, and is a relatively accurate thermal analysis method. In the research, a DSC3 instrument of Mettler Toledo is adopted to scan a sample, the temperature interval is-70-250 ℃, and the heating rate is 10 ℃/min.

The test conditions were: sample weight 0.8 to 1.2mg, nitrogen atmosphere, cycling temperature:

the temperature rise process is carried out at 30-180 ℃,10 ℃/min and 50ml/min of nitrogen, and the heat history is eliminated;

keeping the temperature at 180 deg.C for 2min, introducing nitrogen gas at 50ml/min, and buffering;

cooling at-10 deg.c/min at 180-30 deg.c and nitrogen 50ml/min, and cooling to crystallize;

keeping the temperature at 30 deg.C for 2min, introducing nitrogen gas at 50ml/min, and buffering;

heating process, 30-180 ℃,10 ℃/min, 50ml/min nitrogen, and melting test.

The half peak width is defined as a straight line parallel to the peak bottom through the middle point of the peak height, and the distance between two intersecting points of the straight line and two sides of the peak is measured in units; the peak height is defined as the longitudinal coordinate value corresponding to the melting peak temperature on the horizontal coordinate of the DSC curve, and the unit is W/g.

The value rule of the half-peak width is as follows (see the attached figure 1 in the specification specifically):

taking a DSC melting curve of the second temperature rise to find a melting peak to be analyzed;

secondly, drawing on a melting peak by referring to the method described in 10.1 in ISO 11357-5 to obtain the following characteristic temperatures;

T_i: the onset of the transition, corresponding to the point at which the DSC curve deviates from the initial baseline;

T_f: an end-of-transition point, corresponding to the point at which the DSC curve returns to the final baseline;

T_ei: extrapolated onset temperature, curve low temperature side pass T_iThe temperature corresponding to the intersection point of the baseline extension line of (a) and the tangent line drawn at the maximum slope of the curve corresponding to the start of the low-temperature side transition;

T_ef: extrapolated end temperature, curve high temperature side pass T_fThe temperature corresponding to the intersection point of the baseline extension line of (a) and the tangent line made at the maximum slope of the curve corresponding to the end of the transition at the high temperature side;

T_p: maximum melting rate, corresponding to the top of the peak;

third warp T_pAs T_eiAnd T_efThe vertical line of the connecting line is the peak height, and the midpoint of the peak height is parallel to T_eiAnd T_efAnd the distance between two intersecting points of the straight line and the two sides of the peak is the half-peak width of the DSC melting peak.

Further, when the DSC melting peak appears in plural, the ratio of the half-peak width/peak height of the DSC melting peak is calculated with the peak having the largest area as a reference.

The polyolefin resin foamed sheet is foamed using an azo foaming agent, and the residual ratio of the azo foaming agent in the finally molded foamed sheet is less than 0.2wt%, preferably less than 0.15wt%, and more preferably less than 0.1 wt%. Azo residue is one of the indispensable items of international environmental protection requirements, in order to meet the requirements of the european union REACH regulations, the residue rate of the azo foaming agent in the finally formed foamed sheet should be less than 0.2wt%, and since the foamed sheet cannot achieve the complete consistency of the azo substance residue rate at each position, the cut portion still has the risk of having a residue rate of more than 0.2wt% when used in a mobile terminal after cutting, the residue rate of the azo foaming agent in the foamed sheet is preferably less than 0.15wt%, and more preferably less than 0.1 wt%.

The polyolefin resin foamed sheet has a closed porosity of 90% or more, i.e., a maximum open porosity of 10%; when the foamed sheet is used as a waterproof sealing body for electronic equipment such as a mobile phone and the like, a large number of independent cell structures are required to prevent dust and water vapor from entering, and when the closed cell rate of the foamed sheet is lower than 80%, the compression stress provided when the foamed sheet is compressed as the waterproof sealing body is reduced and is insufficient to meet the waterproof requirement, so that the closed cell rate of the foamed sheet is preferably more than 80%, and more preferably more than 90%.

The foamed sheet has a TD average bubble pore diameter of 50 to 350 μm and an MD average bubble pore diameter of 50 to 350 μm; the foamed sheet is required to be die-cut into pieces suitable for internal parts of electronic equipment such as a camera, an earphone, a power supply key and the like in the using process, the size of the foamed sheet used at the positions is generally small, the cutting width of the foamed sheet is 500-1000 mu m, defective products of through holes are easily generated when the diameter of a foam hole of the foamed sheet is too large, the waterproof performance of the foamed sheet is influenced, and the risk that the residual rate of an azo foaming agent is too high when the diameter of the foam hole of the foamed sheet is too small is caused, so that the TD average foam hole diameter of the foamed sheet is 50-350 mu m, and the MD average foam hole diameter is 50-350 mu m.

The polyolefin resin foamed sheet has a 25% compressive strength of 50 to 650 kPa and an MD tensile strength of 1 to 16 MPa.

The invention also discloses a method for preparing the polyolefin resin foamed sheet, which comprises the steps of taking resins with different molecular weights, different types and different proportions as matrix resins, adding 2-10 wt% of azo foaming agent and other auxiliary agent raw materials, mixing, adding into a high-speed mixer, mixing to obtain a mixture, banburying, crosslinking, foaming and extruding to obtain the foamed sheet.

The resin is preferably two or more of a polyethylene homopolymer or a polyethylene copolymer.

The invention also discloses a waterproof application of the polyolefin resin foamed sheet in electronic products; the electronic product comprises: intelligent mobile communication equipment, notebook computers, electronic books, tablet terminals, game equipment and cameras; the polyolefin resin foaming sheet is applied between a printed circuit board and a cover plate of an electronic product or between an image display part and a display glass plate through the steps of die cutting, gluing, adhering, sealing and shaping.

The invention has the beneficial effects that:

the applicant has found through extensive research that, in the case of a polyolefin resin foamed sheet, the relationship between the half-peak width and the peak height of a DSC melting peak is closely related to the compatibility of different resin mixtures in the resin foamed material, thereby affecting the properties of the polyolefin resin foamed material, such as surface roughness, which are closely related to degumming performance and waterproof performance. If the ratio of the half-peak width to the peak height of the DSC melting peak is too low, the resin compatibility is good, the surface roughness is low, and the surface waterproof effect is good, but the low surface roughness causes the degumming performance of the polyolefin resin foaming material to be reduced, so that the degumming phenomenon is easy to generate. On the other hand, if the ratio of the half-value width of the DSC melting peak to the peak height is too high, this means that the compatibility between resins is poor, resulting in high surface roughness of the polyolefin resin foam, which has the advantage of being less likely to come unstuck, but it may cause deterioration in surface water resistance. Accordingly, the present invention has been found that by controlling the ratio of the half width of the melting peak to the peak height of the DSC melting peak of the polyolefin resin foam sheet within the above-mentioned appropriate range, the present invention can achieve a balance between degumming and water repellency while achieving excellent water repellency of the polyolefin resin foam material without causing degumming.

Drawings

FIG. 1 is a schematic view of a DSC melting peak curve.

Detailed Description

The technical solution of the present invention will be further described in detail with reference to specific embodiments. The following examples are merely illustrative and explanatory of the present invention and should not be construed as limiting the scope of the invention. All the technologies realized based on the above-mentioned contents of the present invention are covered in the protection scope of the present invention.

[ polyolefin resin base Material ]

Factors influencing the compatibility of the resin are many, and the types of different resins, the difference of molecular weights of different resins, the difference of addition ratios of different resins and the like have important influence on the compatibility of the resin, so that the molecular chain structure, the regularity, the crystallization capacity, the surface roughness and the like of the prepared foamed sheet polymer are influenced, and finally, the degumming performance and the waterproof performance of the foamed sheet polymer are influenced. The relationship between the half-value width and the peak height of the DSC melting peak can reflect the difference of the compatibility of the resin, thereby reflecting the difference of the degumming performance and the waterproof performance of the polyolefin resin foaming material. In addition, the specific preparation conditions such as extrusion temperature, extrusion rotation speed, crosslinking irradiation energy, crosslinking irradiation dose and the like also affect the properties such as surface roughness of the finally obtained polyolefin resin foamed sheet to a certain extent, so that the differences of the half-peak width and the peak height of a DSC melting peak are reflected, and the differences of the degumming performance and the water resistance performance of the polyolefin resin foamed material are finally reflected.

According to the invention, by controlling the types and the proportions of the resins with different molecular weights, adjusting the polarity difference of the resins with different molecular weights and different numerical value proportions, and properly adjusting the extrusion temperature, the extrusion rotating speed, the crosslinking irradiation energy, the crosslinking irradiation dose and other preparation conditions, the ratio of the half-peak width to the peak height of the DSC melting peak obtained by final preparation is in a certain range, and the balance of degumming and waterproof performance is finally realized.

The invention also discloses a method for preparing the polyolefin resin foamed sheet, which comprises the steps of taking resins with different molecular weights, different types and different proportions as matrix resins, adding 2-10 wt% of azo foaming agents and other auxiliary raw materials, mixing, adding into a high-speed mixer, mixing to obtain a mixture, carrying out refining, extrusion and crosslinking to obtain a foamed master slice, and then carrying out foaming to obtain the foamed sheet.

Examples of the polyolefin resin constituting the foamed sheet include polyethylene resins; a polypropylene-based resin; olefin copolymers such as ethylene-vinyl acetate copolymer (EVA), ethylene-methyl acrylate copolymer (EMA), and ethylene-butyl acrylate copolymer (EBA), EPDM, polyethylene/polypropylene rubbers, and the like; the polyethylene resin is not particularly limited, and examples thereof include Very Low Density Polyethylene (VLDPE), Low Density Polyethylene (LDPE), medium density polyethylene, High Density Polyethylene (HDPE), Linear Low Density Polyethylene (LLDPE), linear medium density polyethylene, and linear high density polyethylene; examples of the polyethylene resin include ethylene homopolymers, ethylene-vinyl acetate copolymers, and ethylene- α -olefin copolymers, and among these, examples of the α -olefin constituting the polyethylene resin include: propylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, 1-octene, etc. The polypropylene-based resin is not particularly limited, and examples thereof include propylene homopolymers, copolymers of propylene and other olefins, and the like; specific examples of the α -olefin constituting the propylene- α -olefin copolymer include ethylene, 1-butene, 1-pentene, 4-methyl-1-pentene, 1-hexene, 1-heptene, and 1-octene.

The resin of the present invention is preferably two or more of a polyethylene homopolymer or a polyethylene copolymer. Among them, two or more of Low Density Polyethylene (LDPE), Linear Low Density Polyethylene (LLDPE), Medium Density Polyethylene (MDPE), High Density Polyethylene (HDPE), ethylene-vinyl acetate copolymer (EVA) polypropylene (PP), ethylene-butene copolymer, and ethylene-octene copolymer (POE) are preferable.

In addition, both molecular weight and molecular weight distribution have a certain influence on the DSC melting peak, and the larger the molecular weight, the narrower the molecular weight distribution, and the sharper the DSC melting peak. The usual Mn molecular weight of the resin, in the case of LDPE, is preferably 20000 to 70000 with a molecular weight distribution MWD of 20 to 50.

The polyolefin resin foamed sheet of the present invention has a DSC melting peak with a half-value width/peak height ratio of 15 to 71 (. degree.C. g/W), preferably 20 to 50 (. degree.C. g/W).

The DSC melting peak test method comprises the following steps:

in the research, a DSC3 instrument of Mettler Toledo is adopted to scan a sample, the temperature interval is-70-250 ℃, and the heating rate is 10 ℃/min.

② a constant temperature process, 180 ℃, 2min, 50ml/min nitrogen, buffering;

heating process, 30-180 ℃,10 ℃/min, 50ml/min nitrogen, and melting test.

T_f: rotating deviceA change end point, corresponding to the point at which the DSC curve returns to the final baseline;

T_ei: extrapolated onset temperature, curve low temperature side pass T_iThe temperature corresponding to the intersection point of the baseline extension line of (a) and a tangent line made at the maximum slope of the curve corresponding to the start of the low-temperature side transition;

T_p: maximum melting rate, corresponding to the top of the peak;

If the ratio of the half-value width of the DSC melting peak to the peak height is too low, for example, less than 15 (DEG C. g/W), it means that the compatibility of the resin is good, and the surface roughness is low, thereby having a good surface water-repellent effect, but such low surface roughness causes a decrease in the degumming performance of the polyolefin resin foam, resulting in easy degumming. On the other hand, if the ratio of the half-value width of the DSC melting peak to the peak height is too high, for example, higher than 71 (. degree. C. g/W), this means that the compatibility between the resins is poor, resulting in a high surface roughness of the polyolefin resin foam to be finally obtained, which has an advantage of being not easily degummed, but causes deterioration of the surface water-repellent property. Therefore, by controlling the ratio of the half-peak width to the peak height of the DSC melting peak within the above-mentioned appropriate range, the present invention can realize good water resistance of the polyolefin resin foam material without degumming, and achieve a balance between degumming and water resistance.

Furthermore, other additives can be added in the mixing and/or extrusion stage to further improve various properties of the polyolefin foamed sheet, and the other additives can be listed as: antioxidants, antibacterial agents, colorants, antistatic agents, fillers, and the like.

[ mixing ]

After the mixing, the components constituting the resin composition are supplied to a kneading apparatus, and melt-kneaded at a temperature lower than the decomposition temperature of the thermal decomposition type foaming agent, and examples of the kneading apparatus used herein include an injection molding machine, an extruder (a single-screw extruder, a twin-screw extruder, etc.), a banbury mixer, a general-purpose kneading apparatus such as a roll, and the like, but an injection molding machine and an extruder are preferable.

The kneading temperature affects the properties such as surface roughness of the polyolefin resin foamed sheet to some extent, and is reflected by the difference between the half-value width and peak height of the DSC melting peak, and the difference between the degumming performance and the water-repellent performance of the polyolefin resin foamed material is reflected. The mixing temperature is preferably 90 to 160 ℃, more preferably 100 to 150 ℃, and further preferably 110 to 135 ℃.

[ extrusion ]

The extrusion device used herein includes, for example, a single screw and a double screw, the extrusion temperature, the extrusion rotation speed, etc. of the single screw and the double screw all have certain influence on the DSC melting peak, for example, the temperature and the rotation speed during the extrusion process are important factors influencing the half-peak width/peak height ratio of the DSC melting peak of the foamed sheet and the azo residue ratio, the temperature setting range of the extruder barrel is preferably 90 to 150 ℃, the temperature setting of the extruder die is preferably 110 to 140 ℃, and various materials, such as resin, foaming agent, etc. which are extruded and molded at too low temperature have uneven mixing, which influences the quality of the foamed sheet, and are expressed as that the half-peak width/peak height ratio of the DSC melting peak is too large and the azo residue ratio of a partial region is too high; however, the temperature setting is too high, which results in that the azo blowing agent is decomposed during the extrusion process and an acceptable sheet-like resin composition cannot be obtained. The rotation speed of the extruder is preferably set to 15 to 25rpm, too low rotation speed lowers the production efficiency, while too high rotation speed has the same problems as the too low temperature setting, the ratio of half-value width of DSC melting peak/peak height is too large, and the azo residue ratio in a partial region is too high. Therefore, the extrusion temperature, the extrusion rotation speed, and the like of the single-screw and double-screw are controlled within appropriate ranges during the preparation process.

[ Cross-linking ]

In the present invention, after the completion of the mixing of the polyolefin-based substrate and other additives, the gelation reaction process, i.e., the crosslinking reaction, may be carried out by a known technique disclosed in the prior art, and may be carried out by a common method such as radiation crosslinking, or by chemical crosslinking, preferably radiation crosslinking. When electron beam irradiation is used as a method for imparting a crosslinked structure to a foamable polyolefin resin sheet, a foamed sheet obtained by foaming the foamable polyolefin resin sheet has fine independent cells and also has excellent surface smoothness.

The radiation crosslinking is performed by irradiating the resin sheet with ionizing radiation such as electron beam, α -ray, β -ray, and γ -ray. The action of ionizing radiation such as alpha beta gamma ray or electron beam with macromolecule produces free radicals of macromolecule, which when compounded with each other produce cross-linking bond. The resin mixed sheet can be simultaneously crosslinked and degraded when irradiated under electron beams, the crosslinking is mainly performed under low irradiation dose, and the main chain of a macromolecule can be broken under high dose, so that the ratio of half-peak width to peak height of a DSC melting peak is influenced. The electron beam is incident into the resin composite sheet, and the collision occurs to cause the electrons to gradually accumulate, so that the absorbed dose of the resin composite sheet increases and then decreases as it goes from the surface to the inside. The difference of the absorbed doses of the two sides of the foaming sheet with low electron beam energy influences the ratio of the half-peak width to the peak height of a DSC melting peak. In order to prepare the polyolefin foamed sheet having a ratio of half-value width of a DSC melting peak to peak height in the range of the present invention, the irradiation energy is preferably 1.4 to 2.0MeV, and the irradiation dose is preferably 5 to 25 Mrad.

The polyolefin-based foamed sheet of the present invention has a crosslinking degree of 20 to 60%, preferably 20 to 50%, more preferably 25 to 40%, within which the flexibility and impact strength can be in a desired state. Meanwhile, the uniformity of the diameters of the bubble holes of the subsequent foaming can be ensured.

In order to promote the crosslinking of the foamable polyolefin resin sheet by the irradiation of the electron beam, a crosslinking assistant may be added to the foamable polyolefin resin sheet. Examples of such a crosslinking assistant include, but are not particularly limited to, divinylbenzene, trimethylolpropane trimethacrylate, 1, 9-nonanediol dimethacrylate, 1, 10-decanediol dimethacrylate, triallyl trimellitate, triallyl isocyanurate, ethylvinylbenzene, neopentyl glycol dimethacrylate, triallyl 1,2, 4-benzenetricarboxylate, 1, 6-hexanediol dimethacrylate, lauryl methacrylate, stearyl methacrylate, diallyl phthalate, diallyl terephthalate, and diallyl isophthalate, and these may be used alone or in combination of two or more.

[ foaming ]

The crosslinked resin composition is heated to a temperature not lower than the decomposition temperature of the foaming agent to foam the composition, and the composition is foamed and molded to obtain a foam. The crosslinked polyolefin resin sheet is heated to a temperature not lower than the decomposition temperature of the thermal decomposition type foaming agent and foamed to produce a foamed sheet having a crosslinked structure obtained by electron beam crosslinking and containing the polyolefin resin and having closed cells. The temperature at which the thermal foaming is carried out differs depending on the decomposition temperature of the thermal decomposition type foaming agent, and is usually 140 to 350 ℃.

[ azo foaming agent ]

As a method for foaming the foamable composition, there are a chemical foaming method and a physical foaming method. The chemical foaming method is a method of forming bubbles by utilizing a gas generated by thermal decomposition of a compound added to the foamable composition, and the physical foaming method is a method of impregnating a low boiling point liquid (foaming agent) into the foamable composition and then volatilizing the foaming agent to form cells. The foaming method is not particularly limited, and a chemical foaming method is preferable. As the foaming agent, a thermal decomposition type foaming agent is preferably used, and for example, an organic or inorganic chemical foaming agent having a decomposition temperature of about 140 to 350 ℃ can be used. Examples of the organic blowing agent include azodicarbonamide, azodicarbonic acid metal salts (such as barium azodicarboxylate), azo compounds such as azobisisobutyronitrile, nitroso compounds such as N, N '-dinitrosopentamethylenetetramine, hydrazine derivatives such as biurea, 4' -oxybis (benzenesulfonylhydrazide) and toluenesulfonylhydrazide, and semicarbazide compounds such as toluenesulfonylsemicarbazide. Examples of the inorganic foaming agent include ammonium sulfate, sodium carbonate, ammonium hydrogen carbonate, sodium hydrogen carbonate, ammonium nitrite, sodium borohydride, and anhydrous monosodium citrate.

From the viewpoint of achieving a balance among fine bubbles, economy, environmental friendliness, and safety, the azo foaming agent is preferably used, and azodicarbonamide is more preferably used. The polyolefin resin foamed sheet of the present invention has a foaming ratio falling within an ideal range of 1.2 to 20cm based on the content of the foaming agent and the control of the foaming temperature³G, preferably 1.5 to 15cm³Per g, particularly preferably from 2 to 10cm³(ii) in terms of/g. If the expansion ratio is 1.2cm³When the foaming ratio is 20cm or less, the flexibility of the foamed sheet cannot be ensured³If the ratio is more than g, the mechanical strength of the foamed sheet is affected.

[ adhesive layer ]

The obtained polyolefin resin foamed sheet is subjected to sizing before being laminated, namely: the pressure-sensitive adhesive layer is formed on one side or both sides, and various methods in the prior art can be applied, for example, a method in which the pressure-sensitive adhesive composition is directly applied to the foam base (direct method), a method in which the pressure-sensitive adhesive composition is applied to an appropriate release surface, the pressure-sensitive adhesive layer is formed on the release surface, and the pressure-sensitive adhesive layer is bonded to the foam base to transfer the pressure-sensitive adhesive layer (transfer method), and the like. The coating can be performed using a known or conventional coater such as a gravure roll coater, a reverse roll coater, a kiss roll coater, a dip roll coater, a bar coater, a knife coater, or a spray coater.

The type of the adhesive constituting the adhesive layer is not particularly limited, and specifically includes: an adhesive layer composed of one or more of known various adhesives such as an acrylic adhesive, a rubber adhesive (natural rubber, synthetic rubber, a mixture thereof, and the like), a silicone adhesive, a polyester adhesive, a urethane adhesive, a polyether adhesive, a polyamide adhesive, and a fluorine adhesive. From the viewpoint of transparency and weather resistance, the pressure-sensitive adhesive layer is preferably formed using an acrylic pressure-sensitive adhesive.

[ thickness ]

In the invention, the thickness of the foaming sheet is 0.06-1.5 mm. If the thickness is less than 0.06mm, the mechanical strength such as breaking strength may be deteriorated, or the sealing property and impact absorbability may be deteriorated. Further, when it is thicker than 1.5mm, it is difficult to use the foamed sheet in electronic equipment which is miniaturized. The thickness of the foam sheet is 0.06mm to 1.5mm, and when it is within this range, various performances required for the foam sheet of the present invention can be improved, and it is preferably used in various electronic devices with a reduced size.

[ practical application ]

The polyolefin resin foaming sheet disclosed by the invention forms a double-sided waterproof adhesive tape, is attached between a printed circuit board and a cover plate of an electronic product or between an image display component and a display glass plate, and is sealed and shaped to play a role in buffering and waterproofing. The electronic product comprises: intelligent mobile communication device, notebook computer, electronic book, tablet terminal, game device, camera.

[ examples and comparative examples ]

The present invention will be described below with reference to some examples, but the present invention is not intended to be limited to these examples.

Example 1:

mixing 40 parts by weight of LDPE resin with the molecular weight of 24000 and the molecular weight distribution of 20 and 60 parts by weight of LLDPE resin with the molecular weight of 18000 and the molecular weight distribution of 15, then adding 3.5 parts by weight of azodicarbonamide, mixing in a high-speed stirrer, then mixing at 120 ℃, then extruding into strip-shaped sheets, controlling the temperature of an extruder barrel to be 120 ℃, the temperature of an extruder die to be 123 ℃, and the extrusion speed to be 19 rpm; then, performing electron ray irradiation on the two sides of the strip-shaped resin sheet to enable the resin sheet to be crosslinked, wherein the irradiation energy is controlled to be 1.5MeV, and the irradiation dose is controlled to be 25 Mrad; the crosslinked resin sheet was continuously fed into a heating furnace at 210 to 340 ℃, and the resin sheet was foamed by heating the heating furnace with an infrared heater, thereby obtaining a polyolefin-based foamed sheet, the relevant structural and performance indexes of which are shown in tables 1 and 2 below.

Example 2:

mixing 60 parts by weight of LDPE resin with the molecular weight of 24000 and the molecular weight distribution of 20 and 40 parts by weight of LLDPE resin with the molecular weight of 18000 and the molecular weight distribution of 15, then adding 4.0 parts by weight of azodicarbonamide, mixing in a high-speed stirrer, then mixing at 120 ℃, then extruding into strip-shaped sheets, controlling the temperature of an extruder barrel to be 110 ℃, the temperature of an extruder die to be 120 ℃ and the extrusion speed to be 15 rpm; then, performing electron ray irradiation on two sides of the strip-shaped resin sheet to enable the resin sheet to be crosslinked, wherein the irradiation energy is controlled to be 1.8MeV, and the irradiation dose is controlled to be 20 Mrad; the crosslinked resin sheet was continuously fed into a heating furnace at 210 to 340 ℃, and the resin sheet was foamed by heating the heating furnace with an infrared heater, thereby obtaining a polyolefin-based foamed sheet, the relevant structural and performance indexes of which are shown in tables 1 and 2 below.

Example 3:

mixing 65 parts by weight of LDPE resin with the molecular weight of 24000 and the molecular weight distribution of 20 and 35 parts by weight of LLDPE resin with the molecular weight of 18000 and the molecular weight distribution of 15, then adding 3.7 parts by weight of azodicarbonamide, mixing in a high-speed stirrer, then mixing at 120 ℃, then extruding into strip-shaped sheets, controlling the temperature of an extruder barrel to be 140 ℃, the temperature of an extruder die to be 120 ℃ and the extrusion speed to be 22 rpm; then, performing electron ray irradiation on the two sides of the strip-shaped resin sheet to enable the resin sheet to be crosslinked, wherein the irradiation energy is controlled to be 1.5MeV, and the irradiation dose is 22 Mrad; the crosslinked resin sheet was continuously fed into a heating furnace at 210 to 340 ℃, and the resin sheet was foamed by heating the heating furnace with an infrared heater, thereby obtaining a polyolefin-based foamed sheet, the relevant structural and performance indexes of which are shown in tables 1 and 2 below.

Example 4:

mixing 50 parts by weight of LDPE resin with the molecular weight of 48000 and the molecular weight distribution of 30 and 50 parts by weight of POE resin with the molecular weight of 150000 and the molecular weight distribution of 6, then adding 4.5 parts by weight of azodicarbonamide, mixing in a high-speed stirrer, then mixing at 120 ℃, then extruding into strip sheets, controlling the temperature of an extruder barrel to be 130 ℃, the temperature of an extruder die to be 125 ℃ and the extrusion speed to be 24 rpm; then, performing electron ray irradiation on the two sides of the strip-shaped resin sheet to enable the resin sheet to be crosslinked, wherein the irradiation energy is controlled to be 1.5MeV, and the irradiation dose is 10 Mrad; the crosslinked resin sheet was continuously fed into a heating furnace at 210 to 340 ℃, and the resin sheet was foamed by heating the heating furnace with an infrared heater, thereby obtaining a polyolefin-based foamed sheet, the relevant structural and performance indexes of which are shown in tables 1 and 2 below.

Example 5:

mixing 40 parts by weight of 48000 parts by weight of LDPE resin with a molecular weight distribution of 30 and 60 parts by weight of POE resin with a molecular weight distribution of 150000 and a molecular weight distribution of 6, then adding 7.7 parts by weight of azodicarbonamide, mixing in a high-speed mixer, then mixing at 120 ℃, then extruding into strip-shaped sheets, controlling the temperature of an extruder barrel to be 130 ℃, the temperature of an extruder die to be 125 ℃ and the extrusion speed to be 24 rpm; then, performing electron ray irradiation on the two sides of the strip-shaped resin sheet to enable the resin sheet to be crosslinked, wherein the irradiation energy is controlled to be 1.5MeV, and the irradiation dose is 10 Mrad; the crosslinked resin sheet was continuously fed into a heating furnace at 210 to 340 ℃, and the resin sheet was foamed by heating the heating furnace with an infrared heater, thereby obtaining a polyolefin-based foamed sheet, the relevant structural and performance indexes of which are shown in tables 1 and 2 below.

Example 6:

mixing 60 parts by weight of 48000 parts by weight of LDPE resin with a molecular weight distribution of 30 and 40 parts by weight of POE resin with a molecular weight distribution of 6, adding 6.4 parts by weight of azodicarbonamide, mixing in a high-speed mixer, mixing at 120 ℃, extruding into a strip-shaped sheet, controlling the temperature of an extruder barrel to be 120 ℃, the temperature of an extruder die to be 120 ℃ and the extrusion speed to be 20 rpm; then, performing electron ray irradiation on the two sides of the strip-shaped resin sheet to enable the resin sheet to be crosslinked, wherein the irradiation energy is controlled to be 1.8MeV, and the irradiation dose is 15 Mrad; the crosslinked resin sheet was continuously fed into a heating furnace at 210 to 340 ℃, and the resin sheet was foamed by heating the heating furnace with an infrared heater, thereby obtaining a polyolefin-based foamed sheet, the relevant structural and performance indexes of which are shown in tables 1 and 2 below.

Example 7:

mixing 80 parts by weight of LDPE resin with the molecular weight of 48000 and the molecular weight distribution of 30 and 20 parts by weight of POE resin with the molecular weight of 150000 and the molecular weight distribution of 6, then adding 6.2 parts by weight of azodicarbonamide, mixing in a high-speed stirrer, then mixing at 120 ℃, then extruding into strip sheets, controlling the temperature of an extruder barrel to be 120 ℃, the temperature of an extruder die to be 120 ℃ and the extrusion speed to be 20 rpm; then, performing electron ray irradiation on two sides of the strip-shaped resin sheet to enable the resin sheet to be crosslinked, wherein the irradiation energy is controlled to be 1.5MeV, and the irradiation dose is 17 Mrad; the crosslinked resin sheet was continuously fed into a heating furnace at 210 to 340 ℃, and the resin sheet was foamed by heating the heating furnace with an infrared heater, thereby obtaining a polyolefin-based foamed sheet, the relevant structural and performance indexes of which are shown in tables 1 and 2 below.

Example 8:

mixing 20 parts by weight of 48000 parts by weight of LDPE resin with a molecular weight distribution of 30 and 80 parts by weight of POE resin with a molecular weight distribution of 6, adding 6.5 parts by weight of azodicarbonamide, mixing in a high-speed mixer, mixing at 120 ℃, extruding into a strip-shaped sheet, controlling the temperature of an extruder barrel to be 105 ℃, the temperature of an extruder die to be 115 ℃ and the extrusion speed to be 18 rpm; then, performing electron ray irradiation on the two sides of the strip-shaped resin sheet to enable the resin sheet to be crosslinked, wherein the irradiation energy is controlled to be 1.8MeV, and the irradiation dose is 10 Mrad; the crosslinked resin sheet was continuously fed into a heating furnace at 210 to 340 ℃, and the resin sheet was foamed by heating the heating furnace with an infrared heater, thereby obtaining a polyolefin-based foamed sheet, the relevant structural and performance indexes of which are shown in tables 1 and 2 below.

Example 9:

mixing 80 parts by weight of LDPE resin with molecular weight of 65000 and molecular weight distribution of 50 and 20 parts by weight of EVA (Taiwan plastic 7320M) resin with molecular weight of 35000 and molecular weight distribution of 35, adding 3.6 parts by weight of azodicarbonamide, mixing in a high-speed stirrer, mixing at 120 ℃, extruding into strip-shaped sheets, controlling the temperature of an extruder barrel to be 140 ℃, the temperature of an extruder die to be 135 ℃ and the extrusion speed to be 20 rpm; then, performing electron ray irradiation on the two sides of the strip-shaped resin sheet to enable the resin sheet to be crosslinked, wherein the irradiation energy is controlled to be 1.5MeV, and the irradiation dose is controlled to be 20 Mrad; the crosslinked resin sheet was continuously fed into a heating furnace at 210 to 340 ℃, and the resin sheet was foamed by heating the heating furnace with an infrared heater, thereby obtaining a polyolefin-based foamed sheet, the relevant structural and performance indexes of which are shown in tables 1 and 2 below.

Example 10:

mixing 90 parts by weight of LDPE resin with molecular weight of 65000 and molecular weight distribution of 50 and 10 parts by weight of EVA resin with molecular weight of 35000 and molecular weight distribution of 35, adding 6.2 parts by weight of azodicarbonamide, mixing in a high-speed stirrer, mixing at 120 ℃, extruding into strip sheets, controlling the temperature of an extruder barrel to be 140 ℃, the temperature of an extruder die to be 135 ℃ and the extrusion speed to be 25 rpm; then, performing electron ray irradiation on two sides of the strip-shaped resin sheet to enable the resin sheet to be crosslinked, wherein the irradiation energy is controlled to be 1.8MeV, and the irradiation dose is controlled to be 23 Mrad; the crosslinked resin sheet was continuously fed into a heating furnace at 210 to 340 ℃ and heated by an infrared heater to foam the resin sheet, thereby obtaining a polyolefin foamed sheet, the structural and performance indices of which are shown in tables 1 and 2 below.

Comparative example 1:

mixing 30 parts by weight of LDPE resin with the molecular weight of 24000 and the molecular weight distribution of 20 and 70 parts by weight of POE resin with the molecular weight of 200000 and the molecular weight distribution of 3, then adding 5.0 parts by weight of azodicarbonamide, mixing in a high-speed stirrer, then mixing at 120 ℃, then extruding into strip-shaped sheets, controlling the temperature of an extruder barrel to be 130 ℃, the temperature of an extruder die to be 130 ℃ and the extrusion speed to be 22 rpm; then, performing electron ray irradiation on the two sides of the strip-shaped resin sheet to enable the resin sheet to be crosslinked, wherein the irradiation energy is controlled to be 1.5MeV, and the irradiation dose is controlled to be 25 Mrad; the crosslinked resin sheet was continuously fed into a heating furnace at 210 to 340 ℃, and the resin sheet was foamed by heating the heating furnace with an infrared heater, thereby obtaining a polyolefin-based foamed sheet, the relevant structural and performance indexes of which are shown in tables 1 and 2 below.

Comparative example 2:

mixing 50 parts by weight of LDPE resin with the molecular weight of 24000 and the molecular weight distribution of 20 and 50 parts by weight of LLDPE resin with the molecular weight of 18000 and the molecular weight distribution of 15, then adding 4.3 parts by weight of azodicarbonamide, mixing in a high-speed stirrer, then mixing at 120 ℃, then extruding into strip-shaped sheets, controlling the temperature of an extruder barrel to be 160 ℃, the temperature of an extruder die to be 145 ℃ and the extrusion speed to be 27 rpm; then, performing electron ray irradiation on the two sides of the strip-shaped resin sheet to enable the resin sheet to be crosslinked, wherein the irradiation energy is controlled to be 1.8MeV, and the irradiation dose is 4 Mrad; the crosslinked resin sheet was continuously fed into a heating furnace at 210 to 340 ℃, and the resin sheet was foamed by heating the heating furnace with an infrared heater, thereby obtaining a polyolefin-based foamed sheet, the relevant structural and performance indexes of which are shown in tables 1 and 2 below.

Comparative example 3:

mixing 80 parts by weight of LDPE resin with the molecular weight of 24000 and the molecular weight distribution of 20 parts by weight with EVA resin with the molecular weight of 35000 and the molecular weight distribution of 35, then adding 2.2 parts by weight of azodicarbonamide, mixing in a high-speed stirrer, then mixing at 120 ℃, then extruding into strip sheets, controlling the temperature of an extruder barrel to be 120 ℃, the temperature of an extruder die to be 130 ℃ and the extrusion speed to be 15 rpm; then, performing electron ray irradiation on two sides of the strip-shaped resin sheet to enable the resin sheet to be crosslinked, wherein the irradiation energy is controlled to be 1.8MeV, and the irradiation dose is 28 Mrad; the crosslinked resin sheet was continuously fed into a heating furnace at 210 to 340 ℃, and the resin sheet was foamed by heating the heating furnace with an infrared heater, thereby obtaining a polyolefin-based foamed sheet, the relevant structural and performance indexes of which are shown in tables 1 and 2 below.

Comparative example 4:

mixing 10 parts by weight of LDPE resin with the molecular weight of 24000 and the molecular weight distribution of 20 and 90 parts by weight of EVA resin with the molecular weight of 35000 and the molecular weight distribution of 35, then adding 8.0 parts by weight of azodicarbonamide, mixing in a high-speed mixer, then mixing at 120 ℃, then extruding into strip-shaped sheets, controlling the temperature of an extruder barrel to be 90 ℃, the temperature of an extruder die to be 100 ℃ and the extrusion speed to be 13 rpm; then, performing electron ray irradiation on the two sides of the strip-shaped resin sheet to enable the resin sheet to be crosslinked, wherein the irradiation energy is controlled to be 1.5MeV, and the irradiation dose is 8 Mrad; the crosslinked resin sheet was continuously fed into a heating furnace at 210 to 340 ℃, and the resin sheet was foamed by heating the heating furnace with an infrared heater, thereby obtaining a polyolefin-based foamed sheet, the relevant structural and performance indexes of which are shown in tables 1 and 2 below.

The test method comprises the following steps:

half-Width/height measurement of 1-DSC melting Peak

heating process, 30-180 ℃,10 ℃/min, 50ml/min nitrogen, and melting test.

firstly, testing to obtain a foaming sheet DSC melting curve, and finding out a melting peak to be analyzed;

T_i: transition onset corresponding to the point at which the DSC curve deviates from the initial baseline

T_f: the end of transition point, corresponding to the point at which the DSC curve returns to the final baseline.

T_ei: extrapolated onset temperature, curve low temperature side through T_iThe temperature corresponding to the intersection point of the baseline extension line of (a) and the tangent line drawn at the maximum slope of the curve corresponding to the start of the low-temperature side transition;

T_p: maximum melting rate, corresponding to the top of the peak;

2-measurement of thickness

SEM observation was performed on the sample, and the thickness thereof was measured. With reference to GB/T6672-2001, measurements are made with a vernier caliper.

3-measurement of Density

The test was carried out according to GB/T40872-2021 test methods for Plastic polyethylene foams.

Measurement of 4-25% compressive Strength

Determination of 5-tensile Strength

The test is carried out according to GB/T528-2009 determination of tensile stress strain performance of vulcanized rubber or thermoplastic rubber.

6-determination of the degree of crosslinking

a. Taking a sample of 100mg from the foamed sheet, and accurately weighing the sample by weight A (mg);

b. the sample was wrapped with a 200-mesh metal mesh, and the metal mesh-wrapped sample was immersed in xylene at 120 ℃ and allowed to stand for 24 hours. Insoluble substances can be collected in the metal mesh by the filtering action of the metal mesh; accurately weighing the weight B (mg) of insoluble substances after vacuum drying;

c. calculating the crosslinking degree (mass%):

degree of crosslinking (% by mass) = 100% × (B/a).

7-Water resistance test

The test method comprises the following steps: cutting a polyolefin foamed sheet into a square frame with the width of 1mm, wherein the length of the outer diameter is 5mm, sticking glue on one side, sticking the glued surface to the middle position of a 15 multiplied by 2.5cm acrylic plate surface, placing foam cotton between two acrylic plates, placing a gasket with the thickness of 40 percent foam cotton on the periphery, fixing the gasket by using screws, vertically placing the gasket in a water tank with the water depth of 30cm, and starting timing.

If no water leakage occurs after 60min, the waterproof effect is excellent, and the judgment is A;

if no water leaks within 30min and water leaks within 30-60 min, the waterproof effect is good, and the judgment is B;

if water leaks within 30min, the waterproof effect is poor, and the judgment is C.

8-testing of degumming Performance

The test method comprises the following steps:

1. placing the foamed sheet and the 3M 610 type test adhesive tape in a constant temperature and humidity box (temperature: 25 ℃, humidity: 50%) for 24 h;

2. cutting the foamed sheet into 25.4mm × 150mm, respectively attaching 3M 610 type test tapes with the width of 25.4mm to two sides, repeatedly pressing the foamed sheet with the attached tapes for 3 times at the speed of 300mm/min by using a standard rolling wheel of 2Kg, and standing in a constant temperature and humidity box (the temperature is 25 ℃, and the humidity is 50%) for 30 min;

3. the two clamps of the tensile machine respectively clamp the adhesive tapes on the two sides of the foamed sheet, the peeling force is tested by moving at 300mm/min, the data of 20mm before and after the removal of the adhesive tapes are removed by software, and the average peeling force is calculated.

The structural and performance indices of the examples and comparative examples are shown in tables 1 and 2:

TABLE 1 structural indices of examples 1-10 and comparative examples 1-4

Examples	Half peak width (. degree. C.)	Peak height (W/g)	Half peak width/peak height (DEG C. g/W)	Thickness (mm)	Density (g/cm)³)	25% compressive Strength (kPa)	MD tensile Strength (MPa)	Degree of crosslinking
									Example 1	26.75	0.38	70.39	0.08	0.62	507.3	14.73	35.77%
Example 2	15.51	0.60	25.85	0.21	0.48	640.7	9.58	37.76%
									Example 3	15.35	0.63	24.37	0.29	0.45	389.1	7.52	36.64%
Example 4	16.37	0.63	25.98	1.08	0.12	74.7	2.0	27.50%
									Example 5	21.98	0.35	62.80	1.42	0.10	56.4	1.93	25.57%
Example 6	25.73	0.43	59.84	0.78	0.13	59.2	2.5	36.73%
									Example 7	13.34	0.47	28.38	0.39	0.14	91.3	3.83	37.64%
Example 8	11.34	0.59	19.22	0.50	0.15	97.6	3.23	49.64%
									Example 9	12.56	0.46	27.30	0.10	0.51	562.8	10.8	30.36%
Example 10	9.75	0.64	15.23	0.31	0.24	201.5	5.24	34.38%
									Comparative example 1	2.39	0.68	3.52	0.10	0.41	75	9.41	37%
Comparative example 2	4.84	0.59	8.21	0.20	0.36	507	8.16	25%
									Comparative example 3	25.00	0.32	78.13	0.25	0.59	326	15.61	50%
Comparative example 4	34.00	0.45	75.56	0.10	0.37	255	9.73	35%

TABLE 2-Performance indices for examples 1-10 and comparative examples 1-4

Examples	Water resistance test	Peeling force (gf)
			Example 1	B	733.89
Example 2	A	487.11
			Example 3	A	436.15
Example 4	A	513.43
			Example 5	B	688.82
Example 6	B	686.71
			Example 7	A	537.69
Example 8	A	397.46
			Example 9	A	532.97
Example 10	A	301.36
			Comparative example 1	A	182.65
Comparative example 2	A	195.03
			Comparative example 3	C	790.79
Comparative example 4	C	778.22

It can be seen that when the ratio of the half-value width of the DSC melting peak to the peak height is too low to be less than 15 (c · g/W), the polyolefin foam material has a good surface water-repellent effect, but the peel strength is low, which leads to easy degumming. When the ratio of the half-value width of the DSC melting peak to the peak height is too high and is higher than 71 (DEG C. g/W), the polyolefin foam material has the advantage of being difficult to degum due to high peeling force, but the surface waterproof performance of the polyolefin foam material is poor. From the above results, it is found that by controlling the ratio of the half-value width of the DSC melting peak to the peak height to be in a suitable range of 15 to 71 (deg.c. g/W), the present invention can achieve both good water resistance and low degumming tendency of the polyolefin resin foam material, and achieve a good balance between the degumming performance and the water resistance.

Industrial applicability:

the polyolefin resin foamed sheet of the present invention can be used for waterproof cushioning in various electronic products, such as smart mobile communication devices, notebook computers, electronic books, tablet terminals, game devices, cameras, wearable electronic devices, and the like.

The present invention can be practiced in other forms than those described above without departing from the scope of the present invention. The embodiments disclosed in the present application are one example, and are not limited to these. The scope of the present invention is to be construed in priority to the description of the appended claims rather than the description of the above specification, and all changes that come within the meaning and range of equivalency of the claims are intended to be embraced therein.

Claims

1. A polyolefin resin foamed sheet having a thickness of 0.06 to 1.5mm and a density of 0.14 to 0.51g/cm³A closed cell ratio of 90% or more, a crosslinking degree of 20% to 50%, and a compressive strength at 25% of 50 to 650 kPa; characterized in that the ratio of half-value width/peak height of DSC melting peak of the foaming sheet is 20-50 (DEG C.g/W).

2. The polyolefin resin foamed sheet according to claim 1, wherein the polyolefin resin foamed sheet has an MD tensile strength of 1 to 16 MPa.

3. The polyolefin resin foamed sheet according to claim 1, wherein the polyolefin resin foamed sheet is foamed using an azo foaming agent, and the residual ratio of the azo foaming agent in the final foamed sheet is less than 0.2 wt%.

4. The polyolefin resin foamed sheet according to claim 3, wherein the residual content of the azo foaming agent in the finally molded foamed sheet is less than 0.15% by weight.

5. The polyolefin resin foamed sheet according to claim 3, wherein the residual content of the azo foaming agent in the finally molded foamed sheet is less than 0.1% by weight.

6. The polyolefin-based resin foamed sheet according to claim 1, wherein the foamed sheet has a TD average cell diameter of 50 to 350 μm and an MD average cell diameter of 50 to 350 μm.

7. The polyolefin resin foamed sheet according to claim 1, wherein the polyolefin resin is at least two selected from the group consisting of a polyethylene homopolymer and a polyethylene copolymer.

8. Use of the polyolefin resin foamed sheet according to any one of claims 1 to 7 for waterproofing in electronic products.

9. The waterproof application according to claim 8, wherein said electronic product comprises: a smart mobile communication device, a laptop, an electronic book, a tablet terminal, a gaming device, a camera, or a wearable electronic device.

10. The waterproof application according to any one of claims 8 to 9, wherein said polyolefin resin foam sheet comprises steps of die cutting, gluing, attaching, sealing, and setting, and is applied between a printed circuit board of an electronic product and a cover plate, or between an image display member and a display glass plate.

11. An intelligent mobile communication device, wherein the polyolefin resin foamed sheet according to any one of claims 1 to 7 is attached between a printed circuit board and a cover plate of the intelligent mobile communication device.